- Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
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Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
- Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
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p. 8987 - 8996
(2021/06/30)
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- Phosphination of Phenol Derivatives and Applications to Divergent Synthesis of Phosphine Ligands
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We describe a general and efficient protocol for the synthesis of organophosphine compounds from phenols and phosphines (R2PH) via a metal-free C-O bond cleavage and C-P bond formation process. This approach exhibits broad substrate scope and excellent functional group tolerance. The synthetic utilities of this protocol were demonstrated by the synthesis of chiral ligands via the various transformations of cyano groups and their applications in asymmetric catalysis.
- Li, Chenchen,Zhang, Kezhuo,Zhang, Minghao,Zhang, Wu,Zhao, Wanxiang
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supporting information
p. 8766 - 8771
(2021/11/20)
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- Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
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The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
- Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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p. 2682 - 2694
(2020/07/30)
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- An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
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The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
- Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
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- A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
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The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
- Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
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- Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero)aromatic bromide
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A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process.
- Li, Chun-Jing,Lü, Jing,Zhang, Zhi-Xun,Zhou, Kun,Li, Yan,Qi, Guang-Hui
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p. 4547 - 4562
(2018/04/20)
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- Palladium-catalyzed C–P(III) bond formation reaction with acylphosphines as phosphorus source
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Palladium-catalyzed C–P(III) bond formation reaction employing acylphosphines as the phosphorus source was developed. Under the optimized conditions, acylphosphines could react with aryl halides directly affording trivalent phosphines in up to 94% yield.
- Yu, Rongrong,Chen, Xingyu,Wang, Zhiqian
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supporting information
p. 3404 - 3406
(2016/07/11)
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- Covalently and non-covalently immobilized clusters onto nanocarbons as catalysts precursors for cinnamaldehyde selective hydrogenation
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Abstract Ru-based nanoparticles were deposited on carbon nanotubes and graphene via an organometallic approach involving mixed-metal clusters modified with appropriate ligands. These ligands allowed either covalent or non-covalent π-π interactions with the carbonaceous surfaces. The immobilized clusters were then coalesced at different temperatures to give carbon-supported nanoparticles of different sizes. The obtained catalysts were tested in the selective hydrogenation of cinnamaldehyde. It was found that the nature of the metal(s), support nature, incorporation method and activation temperature all had a profound influence on activity and selectivity. Interestingly, the selectivity could be shifted from cinnamyl alcohol (COL) to hydrocinnamaldehyde (HCAL) by changing the reaction solvent. The best catalysts gave a very high selectivity in cinnamyl alcohol, which is not the more thermodynamically favored product, and could be reused several times without loss of activity or selectivity.
- Vriamont, Charles,Haynes, Tommy,McCague-Murphy, Emily,Pennetreau, Florence,Riant, Olivier,Hermans, Sophie
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p. 389 - 400
(2015/06/30)
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- Catalysis with gold complexes immobilised on carbon nanotubes by π-π Stacking interactions: Heterogeneous catalysis versus the boomerang effect
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A new pyrene-tagged gold(I) complex has been synthesised and tested as a homogeneous catalyst. First, a simple 1,6-enyne was chosen as a model substrate for cyclisation by using different solvents to optimise the reaction conditions. The non-covalent immobilisation of our pyrene-tagged gold complex onto multi-walled carbon nanotubes through π-π stacking interactions was then explored to obtain a supported homogeneous catalyst. The heterogenised catalyst and its homogeneous counterpart exhibited similar activity in a range of enyne cyclisation reactions. Bearing in mind that π-π interactions are affected by temperature and solvent polarity, the reuse and robustness of the supported homogeneous catalyst was tested to explore the scope and limitations of the recyclability of this catalyst. Under the optimised conditions, recyclability was observed by using the concept of the boomerang effect. Copyright
- Vriamont, Charles,Devillers, Michel,Riant, Olivier,Hermans, Sophie
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p. 12009 - 12017
(2013/09/23)
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- Catalysts for Suzuki polycondensation: Ionic and "quasi-ionic" amphipathic palladium complexes with self-phase-transfer features
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Poly(9,9-dioctylfluorene) (PFO) with Mn values above 100 000 g mol-1 in a toluene/water system and Mn values up to 600 000 g mol-1 in a THF/water system has been obtained by improved Suzuki polycondensation using a new kind of amphipathic palladium catalyst with self-phase-transfer features, which could overcome the disadvantage caused by the immiscible biphasic mixture and accelerate the transmetalation step (see figure). Copyright
- Li, Jing,Fu, Hongwei,Hu, Pan,Zhang, Zilong,Li, Xiao,Cheng, Yanxiang
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supporting information
p. 13941 - 13944,4
(2020/09/16)
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- Fluoride catalyzed P-aryl-coupling - A mild approach to functionalized arylphosphines
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Functionalized triaryl- and diarylalkylphosphines are accessible in high yields following a mild fluoride catalyzed phosphorous-carbon coupling protocol starting from fluoroarenes and silylated phosphines. The reaction requires a minimum of solvent and ca
- Reis, Andreas,Dehe, Daniel,Farsadpour, Saeid,Munstein, Isabel,Sun,Thiel, Werner R.
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supporting information; experimental part
p. 2488 - 2495
(2012/01/04)
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- 'Click' Dendritic phosphines: Design, synthesis, application in Suzuki coupling, and recycling by nanofiltration
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A new synthetic route towards stable molecular-weight enlarged monodentate phosphine ligands via 'click' chemistry was developed. These ligands were applied in the Pd-catalyzed Suzuki-Miyaura coupling of aryl halides and phenyl boronic acid. The supported systems show very similar activities compared to the unsupported analogues. Moreover, recycling experiments by means of nanofiltration using ceramic nanofiltration membranes demonstrate that these systems can be recovered and reused efficiently.
- Janssen, Michele,Mueller, Christian,Vogt, Dieter
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supporting information; experimental part
p. 313 - 318
(2009/10/20)
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- Homolytic substitution at phosphorus for the synthesis of alkyl and aryl phosphanes
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(Chemical Equation Presented) A transition-metal-free radical phosphonation using Me3SnPPh2 and the less toxic Me 3SiPPh2 is reported. These readily available reagents react highly efficiently with primary and secondary alkyl radicals. Moreover, aryl radicals and tertiary alkyl radicals are phosphonated with Me 3SnPPh2 (see scheme; R = aryl, alkyl, vinyl; X = 1, Br, OC(S)imidazolyl). DFT calculations provide insights into the mechanism of the reaction.
- Vaillard, Santiago E.,Mueck-Lichtenfeld, Christian,Grimme, Stefan,Studer, Armido
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p. 6533 - 6536
(2008/09/17)
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- Radical phosphination of organic halides and alkyl imidazole-1- carbothioates
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Taking advantage of a radical-based methodology, mild and chemoselective phosphination reactions of organic halide and alkyl imidazole-1-carbothioates have been developed. The mild reaction conditions allow labile functional groups to survive during the reaction. Copyright
- Sato, Akinori,Yorimitsu, Hideki,Oshima, Koichiro
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p. 4240 - 4241
(2007/10/03)
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- Synthesis of aryl phosphines via phosphination with triphenylphosphine by supported palladium catalysts
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The palladium catalyzed phosphination of functionalized aryl bromides, triflates, and chlorides with triphenylphosphine to yield aryldiphenylphosphines was catalyzed by thermally stable palladium catalysts supported on charcoal and aluminia. The addition
- Wang, Yanchun,Lai, Chi Wai,Kwong, Fuk Yee,Jia, Wen,Chan, Kin Shing
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p. 9433 - 9439
(2007/10/03)
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- Application of palladium-catalyzed Pd-aryl/P-aryl exchanges: Preparation of functionalized aryl phosphines by phosphination of aryl bromides using triarylphosphines
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Palladium-catalyzed Pd-aryl/P-aryl interchange reaction was applied in the synthesis of various functionalized arylphosphines. This phosphination used inexpensive, readily available and air stable triarylphosphines as the phosphinating agents. Broad functional groups were compatible including keto, aldehyde, ester, nitrile, ether, chloride, pyridyl and thiophenyl groups. Halides were found to be good promoter for the rates and yields of the reaction.
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Chan, Kin Shing
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p. 5635 - 5645
(2007/10/03)
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- Palladium-catalyzed phosphination of functionalized aryl triflates
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Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with man
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Tian, Yuan,Chan, Kin Shing
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p. 10295 - 10305
(2007/10/03)
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- Solvent-free palladium-catalyzed phosphination of aryl bromides and triflates with triphenylphosphine
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Palladium-catalyzed phosphination of substituted aryl bromides and triflates using triphenylphosphine as the phosphinating agent was developed using solvent-free conditions. This operationally simple method tolerates ketone, aldehyde, ester, nitrile and e
- Kwong, Fuk Yee,Lai, Chi Wai,Chan, Kin Shing
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p. 3537 - 3539
(2007/10/03)
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- Palladium-catalyzed biaryl-coupling reaction of arylboronic acids in water using hydrophilic phosphine ligands
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Hydrophilic phosphine ligands possessing a carbohydrate side-chain, such as N-(4-diphenylphosphinophenyl)methyl gluconamide (9), N-[4-(2′-dicyclohexylphosphinobiphenyl)phenylmethyl] gluconamide (10), and N-[4-(2′-di-t-butylphosphinobiphenyl)]phenylmethyl gluconamide (11), were newly synthesized to carry out palladium-catalyzed biaryl coupling of arylboronic acids in a single aqueous medium. The catalyst prepared in situ from Pd(OAc)2 and 10 exhibited a higher efficiency than that of 9, 11, Ph2P(m-C6H4SO3Na) (TPPMS) or P(m-C6H4SO3Na)3 (TPPTS) for representative aryl bromides, chlorides, or triflates. The catalyst prepared in situ from Pd(OAc)2 (0.001mol%) and 10 (0.002mol%) achieved 96,000 TON in the reaction of p-tolylboronic acid with 4-bromoacetophenone in water.
- Nishimura, Masato,Ueda, Masato,Miyaura, Norio
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p. 5779 - 5787
(2007/10/03)
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- Synthesis of aryl phosphines by phosphination with triphenylphosphine catalyzed by palladium on charcoal
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The palladium-catalyzed phosphination of aryl bromides and triflates by phosphination with triphenylphines to yield aryl phosphines was catalyzed by the thermally stable catalyst palladium on charcoal.
- Lai, Chi Wai,Kwong, Fuk Yee,Wang, Yanchun,Chan, Kin Shing
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p. 4883 - 4885
(2007/10/03)
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- A novel synthesis of functionalised tertiary phosphines by palladium catalysed phosphination with triarylphosphines
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The palladium catalysed Pd-aryl/P-aryl exchange was applied in the synthesis of various functionalised phosphines from their corresponding substituted aryl triflates using triarylphosphines as the phosphinating agents. This method tolerated many functional groups including ketone, aldehyde, ester, nitrile, methyl ether, pyridyl and chloride groups. (C) 2000 Elsevier Science Ltd.
- Kwong, Fuk Yee,Lai, Chi Wai,Tian, Yuan,Chan, Kin Shing
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p. 10285 - 10289
(2007/10/03)
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- A general synthesis of aryl phosphines by palladium catalyzed phosphination of aryl bromides using triarylphosphines
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Palladium catalyzed phosphination of substituted aryl bromides using triarylphosphines as the phosphinating agents has been developed; this method tolerates ketone, aldehyde, ester, nitrile, ether and chloride functional groups.
- Kwong, Fuk Yee,Chan, Kin Shing
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p. 1069 - 1070
(2007/10/03)
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- A palladium-catalyzed biaryl coupling of arylboronic acids in aqueous media using a gluconamide-substituted triphenylphosphine (GLCAphos) ligand
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A water-soluble phosphine ligand, N-(4-diphenyl-phosphino)phenylmethyl gluconamide (GLCAphos), was newly synthesized to perform the palladium- catalyzed biaryl coupling of arylboronic acids in a single aqueous media. The catalyst prepared from GLCAphos revealed higher activity than that synthesized from Ph2P(m-C6H4SO3Na) or P(m-C6H4SO3Na)3 for various haloarenes.
- Ueda, Masato,Nishimura, Masato,Miyaura, Norio
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p. 856 - 858
(2007/10/03)
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- Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides
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Nickel-catalysed electrochemical cross-coupling between aryl- or heteroaryl-halides and chlorodiphenylphosphine or dichlorophenylphosphine affords tertiary phosphines in good to high yields.
- Budnikova, Yulia,Kargin, Yuri,Nedelec, Jean-Yves,Perichon, Jacques
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- Nucleophilic phosphanylation of fluoroaromatic compounds with carboxyl, carboxymethyl, and aminomethyl functionalities - An efficient synthetic route to amphiphilic arylphosphanes
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Chiral- and multiply-carboxylated phosphanes and phosphanyl derivatives of benzoic and phthalic acids (1-9) are accessible in high yields by nucleophilic phosphanylation of potassium or lithium salts of commercially available fluorobenzoic and 3-fluorophthalic acids with Ph2PH, Ph2PK, PhPLi2, Ph(K)P-(CH2)3-P(K)Ph in superbasic media (DMSO/KOH) or in THF and DME. The hitherto unknown phosphanylphenylacetic acids (10-13) and phosphanylbenzylamines RR′P-C6H4-CH2-NH2 (14-19, R, R′ = H, Me, Ph) with unsubstituted amino groups were also synthesized by this method. The diphenylphosphanyl derivatives 14-16 (R, R′ = Ph) are accessible by an alternative method involving LiAlH4 reduction of the phosphanylbenzonitriles (20-22), which were obtained in high yields by nucleophilic phosphanylation of the corresponding fluoro- or chlorobenzonitriles. The novel bidentate phosphanylbenzonitrile 23 has also been obtained using this synthetic route. All compounds were completely characterized by elemental analysis, NMR spectroscopy, and mass spectrometry.
- Hingst, Martin,Tepper, Michael,Stelzer, Othmar
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- A new synthesis of hydrophilic carboxylated arylphosphines
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An efficient synthetic procedure for the preparation of versatile functionally substituted arylphosphines from commercially available starting materials is reported together with alternative routes for (carboxyphenyl)diphenyl phosphines.
- Ravindar,Hemling,Schumann,Blum
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p. 841 - 851
(2007/10/02)
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